The calcium aluminate leaching residues(CALR), which were from the process of polyaluminum chloride production, were activated by hydrochloric acid and sodium hydroxide, respectively, and the adsorption properties CALR and activation products on heavy metals in zinc metallurgical wastewater were researched. The change of structure, specific surface area, pore structure of CALR and activation products were investigated. The effects of pH value, adsorption time and heavy metal concentration on its adsorption performance were analyzed. The industrial experiments were also conducted with NaOH activation products(NaOH AP). The results show that the structure changes from island to layer after CALR are activated by HCl and NaOH. The specific surface areas of CALR, HCl activation products(HCl AP) and NaOH AP are 21.8, 63.1, 28.1 m2/g, respectively, the BJH pore diameters of CALR, HCl activation products (HCl AP) and NaOH AP are 36.06, 43.54, 236.35 nm, respectively, and the pore volumes of CALR, HCl activation products (HCl AP) and NaOH AP are 0.03, 0.09, 0.14 cm3/g, respectively. According to Langmuir isotherm, the saturation Cd2+, Zn2+, As(V) adsorption capacities are 21.8, 497.57, 2.45 mg/g, respectively, the adsorption capacities of HCl AP are 3.44, 516.32, 2.04 mg/g, respectively, and the adsorption capacities of NaOH AP are 7.64, 526.32, 4.72 mg/g, respectively, when pH value is 8, the adsorption temperature is 25℃, adsorption time is 150 min. The industrial experiment results show that the chemical adsorption is in possession of adsorption process and that the concentrations of Cu2+, Pb2+, Zn2+, Cd2+, and As(V) in zinc metallurgical wastewater treated with NaOH AP decrease from 1.68, 13.12, 147.00, 15.14, and 1.56 mg/L to 0.01, 0.05, 0.52, 0.03, and 0.02 mg/L, respectively. The water qualities reach up to the "Emission Standard of Pollutants for Lead and Zinc Industry" (GB25466-2010). © 2019, Science Press. All right reserved.